Chromium containing mixed azo dyes



United States Patent 0,400/ 6 US. Cl. 260-145 Int. Cl. 'C09b 31/00 5Claims This invention relates to a process for the production ofheterogeneous metal complex dyes, which consists in reacting with anamount of a chromium compound yielding at least 1 equivalent of chromiuma mixture of n moles of a disazo dye of formula and (2-n) moles of amonoazo dye of formula cyl (H) where n represents a value between 0.5and 1.5, preferably between 0.8 and 1.2, A an aryl radical, and X acarboxylic or sulphonic acid or sulphonic acid amide group. Theindividual dyes of Formulae I and II in the form of their chromiumcomplexes are known. In Formula I, A represents preferably a phenyl ornaphthyl radical. These radicals may be further substituted, for example by alkyl or alkoxy, e.g., with 1 to 6 carbon atoms, which may besubstituted, or by halogen atoms such as chlorine, bromine or fluorineatoms. In the especially preferred phenyl radical the substituent X mayoccupy the ortho-, metaor para-position in respect to the azo group.When X represents a sulphuric acid amide group it may be substituted,for example by a hydroxyalkyl radical. The acyl radicals in Formulae Iand II are preferably lower alkylcarbonyl or sulphonyl radicals, inparticular alkylcarbony radicals having 1 to 4 C atoms; the alkylradicals of the alkylcarbonyl groups may be substituted, primarily byhalogen such as chlorine, bromine or fluorine, or by hydroxyl or alkoxygroups with, for example, 1 to 4 C atoms. Examples of other suitableacyl radicals are lower alkoxy carbonyl groups whose alkyl radicals maybe substituted, for example by lower alkoxy groups.

The metallisation reaction can be carried out in one stage, that is tosay, the dyes of Formulae I and II can be metallised simultaneously. Itcan be conducted in aqueous solution or in an organic medium, forexample formamide, or in the concentrated aqueous solution of an alkalimetal salt of a lower aliphatic monocarboxylic acid at temperatures of80 to about 130 C. An amount of a chromium-yielding agent containing atleast 1 but preferably less than 2 gram equivalents of chromium isallowed to act upon 2 moles of the mixture of dyes.

Examples of suitable chromium compounds are chromic fluoride, chromicsulphate, chromic formate, chromic acetate, chromic potassium sulphateand chromic ammonium sulphate. The chromates also, for example sodium orpotassium chromate or bichromate, are very suitable, especially instrongly caustic-alkaline medium, in which case reducing substances canbe added if necessary.

It is of special advantage to perform the metallising reaction inaqueous or alkali medium in the presence of compounds which maintain themetal dissolved in complex combination, for example tartaric, citric,lactic or salicylic acid.

Alternatively, the metallising reaction can be carried out in twostages, the 1:1 chromium complex compound of a dye of Formula I or 11being produced first and this reacted with the second metal-free dye toform the 1:2 complex. One suitable procedure is to react one of the twodyes, most expediently the one of Formula I which contains a sulphonicacid group, in acid medium with an excess of the trivalent chromium suchas chromium formate, chromium sulphate or chromium fluoride, either atthe boil or at a temperature superior to the boil. The dyes which arefree from sulphonic acid groups are converted into the 1:1 chromiumcomplexes preferably in an organic solvent, for example ethanol orformamide.

The reaction of the 1:1 metal complexes with the metalfree dyes can beeffected in aqueous, neutral or weakly alkaline medium at normal orelevated temperature, e.g., in the temperature range of to 130 C.

The dyes thus formed are 1:2 heterogeneous chromium complexes. Inaqueous solution they are suitable for dyeing leather and for dyeing,padding or printing animal fibres, for example wool or silk, andsynthetic polyamide fibres.

They are well soluble in polar solvents, for example acetone, ethanoland ethyl acetate, and in these solutions they are suitable for dyeingand printing leather and for dyeing fibre-forming materials likewisedissolved in organic solvents. In these materials they give olive greenshades of good light and wet fastness.

Wool, silk and polyamide fibres are dyed or printed preferably from aweakly acid, neutral or wealkly alkaline medium, for example in thepresence of acetic acid, ammonium sulphate or sodium metaphosphate. Theycan also be dyed from an acetic acid to neutral bath in the presence ofleveling agents, of which polyoxethylated fatty amines and mixtures ofthese and alkylpolyglycol ethers are examples, at temperatures of toabout 130 C., e.g., 108 C. or more particularly 98-102 C. withoutpressure and 120'130 C. with pressure for polyamide fibres.

The dyeing obtained have good fastness to light and Wet tests such aswashing, milling, perspiration, water, sea water, acids, alkalis,carbonising, stoving, cross dyeing and decatising. They are stable toheat and show little sensitivity to metals.

In the following examples the parts and percentages are by weight andthe temperatures in degrees centigrade.

EXAMPLE 1 28.9 parts of the disazo compound obtained by couplingdiazotised 3' amino 4' hydroxy-l,l'-azobenzene-3-sulphonic acid amidewith l-carbo-(2'-ethoxy) -ethoxyamino- 7-hy-droxynaphthalene and 24.9parts of the monoazo compound obtained by coupling diazotised2-amino-1-hydroxy- 4-nitro-6-acetylaminobenzene with1-canbo-(2'-ethoxy)- ethoxyamino-7-hydroxynaphthalene are stirred into200 parts of formamide. After the addition of 25 parts of chromicammonium sulphate (NH Cr(SO -12H O) the mixture is stirred at 100-110until the unmetallised starting dyes are no longer indicated. It is thendiluted with 600 parts of 20% sodium chloride solution and the chromiumcomplex compound formed is precipitated, isolated and purified bydissolving in aqueous alkaline medium, reprecipitation with common saltand filtration. After drying and grinding, the dye is obtained as a darkpowder which dissolves in water to give olive green soluexcellent lightfastness and good fastness to milling, washing, perspiration, water,heat, acids, chlorine, carbonising, stoving and cross dyeing.

A dye with similar properties is obtained when 18.5 parts of theaforenamed disazo dye and 33.5 parts of the aforenamed monoazo dye arereacted with a chromium compound in accordance with the proceduredescribed in Example 1.

TABLE Example Shade No. Disazo dye Monoazo dye Metal of wool dyeing 31-(3'-amino-4'-hydr0xy)-phenyl-azo- 2-amino-l-hydroxy-i-nitro-fi-acetyl-Cr Olive.

naphthaleneA-sulphonic acid 1- amino-benzene 1-carbo-(2-acetylamino-7-hydroxy naptlialene.ethoxy)-ethoxyamino-7-hydroxynaphthalene.

4 1-(3-amino-4-hydroxy)-phcnyl- 2-amino1-hydroxyi-nitro-fi-acctyl- CrD0.

azonaphthalcnc5-sulphonic acid amino-benzenel-dimethyll-carbethoxyamino-7-hydroxyamino-sulphonyl-amino-7-hydroxynaphthalcne.naphthalene.

5 1-(3-amino-4'-hydroxy)-pheny1- 2-amino-1-hydroxy-4-nitro-6-acetyl- CrD0.

azonaphthalcne-5-sulphonic acid amino-benzene 1-acetylamino7-l-carbo-(2-ethoxy)-ethoxy-amino-7- hydroxynaphthalene.hydroxynaphthalene.

6 2-(3-aruin0-4-hydroxy)-phenyl-azo-2-amino-1-hydroxyi-nitro-fi-carbeth- Cr Do.

naphthalene-G-sulphonic acid 1- oxyarninobenzenel-acetylaminocarbomethoxyamino-7-hydroxy- 7-hydroxynaphtha1ene.naphthalene.

7 1-(3-amino-4-hydroxy)-phenyl-azo- 2-amino-l-hydroxy-4-nitro-6-acetyl-Cr Do.

naphthalene-G-sulphonic acid 1- aminobenzcnel-carbethoxypropionylamino-7-hydroxyamino-7-hydroxynaphthalene.naphthalene.

8 3'-amino-4'-hydroxy-1,1-azobenzene- 2-amino-1-hydroxy-4-nitro6acetyl-Cr D0.

4-sulphonic acid l-benzoylaminobenzene 1-carbo-(2-amino-7-hydroxynaphthalene. ethoxy)-cthoxyamino-7-hydr0xynaphthalene.

9 3'-amino-4-hydroxy-l,1-azobenzene- 2-amino-1-hydroxy-4-nitro-(Hormyl-Or D0.

2-sulphonic acid 1-acetylamino-7- aminobenzenc 1-acety1amin0-7-hydroxynaphthalene. hydroxynaphthalene.

10 3-an1ino-4'-hydroxy-1,1-azobenzene-2-amino-1-hydroxy-4-nitro-6-acetyl- Cr D0.

Z-carbonic acid l-carbethoxyaminobenzene l-carbo-(2-amino-7-hydroxy-naphthalene. ethoxy)-ethoxy-amino-7-hydroxynaphthalene.

11 3-amino-4-hydroxy-2-methyl-l,1- do Cr D0.

azobenzene-fi-sulphonic acid 1- ilacetylamino-7-hydroxynaphthaene.

12 3-an1ino4-hydroxy-1,l-azobenzenedo Cr Do.

3-sulphonic acid-methyl-amide 1- acctylarnino-7-hydroxynaphthaene. 131-(3-amino-4-hydroxy-phenylazo- 2-amino'1hydrcxy-4-n1tro-6-acetyl- CrD0.

naphthalene-4-sulphonic acid 1-methansulphonylaminoJ-hydroxynaphthalene.

aminobenzene l-benzenesul- 1phonyl-amino7-hydroiiynaphthaene.

It can also be used for pigmenting surface coatings such as vinyl andnitrocellulose lacquers in olive green shades.

A dye with similar properties is obtained when 43.2 parts of theaforenamed disazo dye and 12.5 parts of the monoazo dye are metallisedin accordance with the particulars given in this example.

EXAMPLE 2 2.7 parts of the disazo compound obtained by couplingdiazotised 1 (3' amino-4'-hydroxy)-phenylazonaphthalene-S-sulphonic acidwith 1-acetylamino-7-hydroxzynaphthalene are stirred in 200 parts ofethylene glycol, with the subsequent addition of parts of chromicammonium sulphate (NH Cr(SO -12H O). The mixture is raised to 130 andheld at this temperature for a few hours, after which the metal-free dyeis no longer indicated. It is allowed to cool to 100, on which 24.9parts of the monoazo compound obtained by coupling 24.9 parts ofdiazotised 2 amino 1-hydroxy-4-nitro-6-acetylaminobenzene with1-carbo-(2-ethoxy)-ethoxyamino-7-hydroxynaphthalene are added, togetherwith 100 parts of formamide. Stirring is continued for a further hour at100. After this time no further metal-free dye is indicated in thereaction mixture. It is diluted with a solution of 100 parts of sodiumchloride in 700 parts of water, on which the dyestuif precipitates. Onisolation it is purified by dissolving in water with the aid of sodiumhydroxide, precipitation with sodium chloride and filtration. On dryingand grounding it is obtained as a dark powder which dissolves in waterwith an olive coloration and dyes wool, silk, leather and polyamidefibres in olive-green shades of APPLICATION EXAMPLE A A dyebath isprepared by dissolving 1 part of the dye obtained according to Example 2in 4000 parts of water at 40-50". parts of previously wetted out woolare entered into the bath, 2 parts of acetic acid are added dropwise,and the bath is raised in 30 minutes to 100 and maintained at the boilfor a further hour. tIhe wool is then removed, rinsed with water anddried. An olive green dyeing is obtained which 'has good light and wetfastness properties.

A dyeing showing the same fastness properties is obtained when the 100parts of wool are replaced by 100 parts of nylon.

APPLICATION EXAMPLE B A solution is prepared with 20 parts of a vinylchloride/ vinyl acetate copolymer, for example Vinylite VMCH (registeredtrademark of Union Carbide, Inc.), 70 parts of methylethylketone and 10parts of ethylene glycol. To this is added a solution of 0.5 part of thedye obtained according to Example 1 in 10 parts of the same lacquer, andfinally the composition is diluted with 25 parts of a 1:1 mixture ofmethylethylketone and cyclohexanone. It is applied to aluminium foil anddried in the air. The coating, which is of olive-green colour, has goodadhesibility, good resistance to wet rubbing, fats and top finishes, andexcellent fastness to light.

Formulae of representative dyes of the foregoing examples are asfollows:

3,432,485 6 EXAMPLE 14 and 1 mol of the azo compound of the formula The1:2 chromium mixed complex of 1 mol of the OH 110 azo-compound of theformula HaC-OC-HN -N=N -OH HO 5 EN Q Q N0: S0zN(OH B02NH: HN

0=l70CzH40C H EXAMPLE 18 and 1 l f th am compound of th f l The 1:2chromium mixed complex of 1 mol of the azo compound of the formula on noHaC-OC-HN N=N H HN HOaSC -N=N N=N EXAMPLE 15 and 1 mol of the azocompound of the formula The 1:2 chromium mixed complex of 1 mol of theazo compound of the formula OH HO OH o HaC-O C--HN N=N =N N=N EN I H038I o=o-o-cH40-c2m Ha I claim: and 1 mol of the azo compound of theformula 1. The 1:2 chromium mixed complex of 1 mol of the azo compoundof the formula 1130-00-11: N=N OH no not 40 QN=N N=N N02 0 l and 1 molof the am compound of the formula 2. The 1:2 chromium mixed complex of 1mol of the azo compound of the formula o= -O-CzH4-O-CzH5 HN EXAMPLE 17(LO-CH; The 1:2 chromium mixed complex of 1 mol of the azo compound ofthe formula and 1 mol of the azo compound of the formula OH OH H0 1150-0C-HN N=N =N N=N HN HOaS HN I l NO 7 8 3. The 1:2 chromium mixed complexof 1 mol of the and 1 mol of the azo compound of the formula azocompound of the formula OH HO I OH HO 8 110,5 N=N N=N I EN N02 8 02N(a):

'5. The 1:2 chromium mixed complex of 1 mol of the JXFCHZ 10 azocompound of the formula HOaS N=N N=N and 1 mol of the formula v 0 HO 1and 1 mol of the azo compound of the rormula HzC-OC-HN N=N OH HO EN 7HaC-OG-HN N=N =C-OCzH4-OCz l 4. The 1:2 chromium mixed complex of 1 molof the References Cited azo compound of the formula v UNITED STATESPATENTS 2,610,175 9/1952 Widmer et a1 260145 OH HO 2,775,581 12/1956Neier et a1. 260'145 N=N N: CHARLES B. PARKER, Primary Examiner.

D. M. PAP'UGA, Assistant Examiner. HOaS HN US. Cl. X.R.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3,432,485

March 11, 1969 Reinhard Neier shown below: Column 1, line 47, "alkylcarbony" should read alkylcarbonyl Coluxr 3, line 55, "hydroxzynaph"should read hydroxynaph- Column 7, lines 1 to 25, that portion of theformula reading (SEAL) Signed and sealed this 24th day of March 1970.Attest:

Edward Fletcher, Jr. WILLIAM E. Attesting Officer Commissioner ofPatents

1. THE 1:2 CHROMIUM MIXED COMPLEX OF 1 MOL OF THE AZO COMPOUND OF THEFORMULA